Respiratory pigments of blood in setting permanent waves



United States Patent RESPIRATORY PIGMENTS OF BLOOD 1N SETTING PERMANENT WAVES Milton H. Schwarz, Morristown, N. J., .and Albert Shansky, Bayside, N. Y., assignors to Turner Hall Corporation, New York, N. Y., a corporation of New York No Drawing. Application August 14, B51, Serial No. 241,882

12 Claims. (Cl. 132-7) This invention relates to permanent waving of hair on the human head. In its preferred embodiment the invention pertains to cold permanent waving, i. e. to permanent waving without an external source of heat.

Conventionally, in cold waving of hair on the human head, the hair is first treated with a softening composition containing, for example, a mercaptan or a sulfite. This composition reduces and thereby disrupts the disulfide bonds of the hair keratin.

The hair is shaped, for example, by winding on rods,

before or after the softening. After both shaping and softening, the disulfide bonds are substantially restored so that the finished hair will have substantially its original elasticity and will retain its altered shape.

It is desirable to neutralize any residual softening composition remaining on the hair after softening since, if a hair softener is allowed to remain in contact with the hair, it will deteriorate the permanent wave whichhas been formed and may impart a bad odor to the hair, especially when the latter is rewetted.

At present, inorganic oxidants, such as hydrogen peroxide and sodium bromate, are employed to restore the hair and to neutralize the softening composition. A serious drawback to such methods of restoring disulfide bonds of hair on the human head is that the oxidation may be carried too far. The disrupted components of keratin are capable of being oxidized to higher states than the original one, and in such cases, loss of hair qualities, change in porosity, brittleness, and harshness will result.

It is a principal object of the present invention to provide novel methods and compositions not subject to the foregoing drawback.

It is another object of the present invention to provide novel methods and compositions for oxidizing reduced keratin of hair on the human head.

It is another object of the present invention to provide methods and compositions for controlled oxidation of reduced keratin of hair on the human head whereby only the original state of oxidation of the hair is attained and not higher states.

It is another object of the present invention to provide methods and compositions of the character described employing as the oxidants substances naturally occurring in living cells.

It is another object of the present invention to provide compositions of the character described which are inexpensive to manufacture.

It is another object of the present invention to provide a method of the character described which is similar to present methods in its manipulative steps so that additional skill is not required to practice the same.

Other objects of the invention in part will be obvious and in part will be pointed out hereinafter.

The invention accordingly consists in the compositions and steps which will be exemplified in the compounds and processes hereinafter described and of which the scope of application will be indicated in the appended claims.

Pursuant to the present invention, oxidizing agents are employed which do not oxidize the reduced (disrupted) keratin beyond the natural (initial) state thereof, but which will etficiently and substantially restore the reduced keratin in a commercially practicable time.

The respiratory pigments, i. e. oxygen-carrying ingredients, of the blood of warm-blooded and cold-blooded animals have been found to be capable of catalyzing the oxidation of certain specific substances in living cells. Pursuant to the instant invention'it has been discovered that these pigments will effect the oxidation of softened hair on the human head to its original state and no further.

The oxygen-carrying ingredients of the blood of warmblooded animals is hemoglobin, and the oxygen-carrying ingredient of the blood of cold-blooded animals is hemocyanin. These pigments are each composed of two groups, one being a prosthetic group and the other being a carrier. It is the prosthetic group in combination with the carrier which gives the pigments their catalytic power.

The prosthetic group of hemoglobin is an iron-porphyrin radical called hematin. The carrier isa protein called globin. Hemocyanin has as its prosthetic group a copperpeptide complex called a hemocuprin. Its protein carrier is a plasma protein of high molecular weight and has not been completely identified.

Hemoglobin will only be active to carry out the present invention below a pH of 7. The reason for this is thought to be that below a pH of 7 the iron-porphyrin radical becomes a hematin, which is active 'as an 0xidizing catalyst. It has been found that hemocyanin works over a wide range of pH, in both acid and alkaline states. The cupric form of a hemocyanin is reduced by the substrate, i. e., the substance to be oxidized, and it is believed that changes in pH have very little influence on the reversible reaction of the cupric to the cuprous state.

The operation of the present invention may be illustrated by the following example: the disulfide bonds of the hair keratin are softened with an'alkaline thioglycollate composition for a long enough time to render the hair plastic. The hair is shaped before or after the softening step. Then, after softening and shaping, a com position containing hemoglobin or hemocyanin is put on the hair for a short time to substantially restore the broken disulfide bonds. Because the oxidation will ceaseat the proper point, the pigment need not be rinsed out and the setting step is simplified.

It'has been observed that the respiratory pigments will function in accordance with the instant invention when present in amounts ranging from merely a trace, e. g., .01% by weight, to as high as their practical limit of water solubility, i. e. about 5% by weight.

In carrying out the softening stepof the instant invention, any mercaptan suitable for hair waving can be used. The presently preferred rnercaptan is thioglycollic acid or a salt thereof, e. g., ammonium thioglycollate. Mercaptans of this type are enumerated in detail in Australian Patent No. 117,071 accepted June 17, 1943. Alternatively, any other well known agent which softens hair by reduction and consequent disruption of the disulfide bonds can be employed, e. g, sodium bisulfite, sodium sulfite, and ammonium hydrosulfide. Examples of oxidizing compositions embodying the present invention follow:

1. Citric acid with disodium acid phosphate buffer ml 500 Hemoglobin "gins" 2% (pH 6.0) Setting time: 20 minutes. 2. gms. of mussel meat comminuted with 200 ml. of water. After filtering of the mix the filtrate contains .066 mg. percent Cu. 200 ml. adjusted to pH 8.0 with sodium hydroxide. Setting time: 20 minutes.

A typical softening composition which can be used to treat the hair prior to the application of any of the setting compositions set forth above is:

lOO ml. of water. 7% by weight thioglycollic acid. Enough ammonia to obtain pH 9.3.

It may be mentioned that a setting composition embodying the present invention also can be used in conjunction with a protein impregnating softening composition such as is described in United States Letters Patent l-Io. 2,540,494 for Permanent Hair Waving issued February 6, 1951. Typical setting compositions used with such a softening composition are:

l. Hemoglobin (bovine) gm 1 Glacial acetic acid ml 5 Dilute to a pint with water.

Setting time: 20 minutes.

2. 200 ml. of the filtrate in Example 2 above.

Adjust to pH 2.0 with acetic acid. Setting time: 20 minutes.

Softening compositions which can be used with these setting compositions are given in said Letters Patent No. 2,540,494.

By way of example there is set forth below a complete hair waving process incorporating the present invention:

1. The hair is blocked off.

2. The hair is wetted with a softening composition.

3. The hair is wound up in curlers.

4. The hair is rewetted with a softening composition.

5. If desired, the hair is covered to permit the temperature to rise.

6. The hair is allowed to stand until the hair is softened as indicated by the wave pattern.

7. The hair is rinsed with lukewarm water.

8. The setting agent is rinsed through the hair for twenty minutes. 7

9. The hair is taken out of the curlers.

10. The setting agent is applied to each curl.

11. If any residual softening or setting composition causes malodor to the hair, the latter may be washed.

It thus will be seen that there are provided compositions and processes which achieve all the objects of the invention and are well adapted to meet the conditions of practical use.

As various possible embodiments might be made of the above invention, and as various changes might be made in the embodiments above set forth, it is to be understood that all matter herein described is to be interpreted as illustrative and not in a limiting sense.

Having thus described the invention, there is claimed as new and desired to be secured by Letters Patent:

1. A setting composition adapted to be used in conjunction with a previously applied composition for dis rupting disulfide bonds of keratin in permanently waving hair on the human head: said setting composition containing a respiratory pigment of blood in an aqueous carrier with a bufiering compound to adjust the pH of the composition to a value between 2 and 8 to effect the oxidation of the disrupted disulfide bonds to and not beyond their original state.

2. A setting composition adapted to be used in conjunction with a previously applied composition for disrupting disulfide bonds of keratin in permanently waving hair on the human head: said setting composition containing hemoglobin in an aqueous carrier with a buffering compound to adjust the pH of the composition to a value between 2 and 7 to effect the oxidation of the disrupted disulfide bonds to and not beyond their original state.

3. A setting composition adapted to be used in conjunction with a previously applied composition for disrupting disulfide bonds of keratin in permanently waving hair of the human head: said setting composition containing hemocyanin in an aqueous carrier with a buffering compound to adjust the pH of the composition to a value between 2 and 8 to effect the oxidation of the disrupted disulfide bonds to and not beyond their original state.

4. A setting composition adapted to be used in conjunction with a previously applied composition for disrupting disulfide bonds of keratin in permanently waving hair on the human head: said setting composition containing a respiratory pigment of blood in an aqueous carrier with a bultering compound to adjust the pH of the composition to a value between 2 and 8 to effect the oxidation of the disrupted disulfide bonds to and not beyond their original state, said respiratory pigment being selected from the group consisting of hemoglobin and hemocyanin.

5. A setting composition adapted to be used in conjunction with a previously applied composition for disrupting disulfide bonds of keratin in permanently waving hair on the human head: said setting composition containing a respiratory pigment of blood in an aqueous carrier with a buffering compound to adjust the pH of the composition to a value between 2 and 8 to effect the oxidation of the disrupted disulfide bonds to and not beyond their original state, said respiratory pigment being present in a concentration up to about 5% by weight.

6. In a method of permanently waving hair on the human head in which the hair is shaped and treated with a softening composition for disrupting disulfide bonds of keratin: that improvement comprising the step of subsequently substantially restoring the softened hair to its original condition by applying to the softened hair a composition containing a respiratory pigment of blood which effects the oxidation of the disrupted disulfide bonds to and not beyond their original state.

7. In a method of permanently waving hair on the human head in which the hair is shaped and treated with a softening composition for disrupting disulfide bonds of keratin: that improvement comprising the step of subsequently substantially restoring the softened hair to its original condition by applying to the softened hair a composition containing hemoglobin which effects the oxidation of the disrupted disulfide bonds to and not beyond their original state.

8. In a method of permanently waving hair on the human head in which the hair is shaped and treated with a softening composition for disrupting disulfide bonds of keratin: that improvement comprising the step of subsequently substantially restoring the softened hair to its original condition by applying to the softened hair a composition containing hcmocyanin which effects the oxidation of the disrupted disulfide bonds to and not beyond their original state.

9. A method of permanently waving hair on the human head, said method comprising softening the hair with a composition which disrupts the disulfide bonds of keratin, shaping the hair, and then substantially restoring the disrupted disulfide bonds by applying to the softened hair a setting composition containing a respiratory pigment of blood which effects the oxidation of the disrupted disulfide bonds to and not beyond their original state.

10. A method of permanently waving hair on the human head, said method comprising softening the hair with a composition which disrupts the disulfide bonds of keratin, shaping the hair, and then substantially restoring the disrupted disulfide bonds by applying to the softened hair a setting composition containing hemoglobin which effects the oxidation of the disrupted disulfide bonds to and not beyond their original state.

11. A method of permanently waving hair on the human head, said method comprising softening the hair with a composition which disrupts the disulfide bonds of keratin, shaping the hair, and then substantially restoring the disrupted disulfide bonds by applying to the softened hair a setting composition containing hemocy- References Cited in the file of this patent UNITED STATES PATENTS 2,261,094 Speakman Oct. 28, 1941 6 2,376,186 Rapkine May 15, 1945 2,425,285 Strickler Aug. 5, 1947 2,540,980 Den Beste Feb. 6, 1951 FOREIGN PATENTS 270,698 Switzerland Dec. 1, 1950 OTHER REFERENCES Anderson: Enzymes and Their Role in Wheat Technology, Interscience Publishers, New York, 1946, pages 175-199.

Whitmore: Organic Chemistry, Van Nostrand, 1937, pages 598-599.

Dorland: American Illustrated Dictionary, W. B. Saunders Co., 1947 (21st edition); entries: Hematocyanin, Hemocyanin, Hemoglobin. 

9. A METHOD OF PERMANENTLY WAVING HAIR ON THE HUMAN HEAD, SAID METHOD COMPRISING SOFTENING THE HAIR WITH A COMPOSITION WHICH DISRUPTS THE DISULFIDE BONDS OF KERATIN, SHAPING THE HAIR, AND THEN SUBSTANTIALLY RESTORING THE DISRUPTED DISULFIDE BONDS BY APPLYING TO THE SOFTENED HAIR A SETTING COMPOSITION CONTAINING A RESPIRATORY PIGMENT OF BLOOD WHICH EFFECTS THE OXIDATION OF THE DISRUPTED DISULFIDE BONDS TO AND NOT BEYOND THEIR ORIGINAL STATE. 